Initiator systems comprising beta-ketone compounds and bonding compositions made therewith

ABSTRACT

The invention provides initiator systems capable of initiating polymerization. More specifically, the invention relates to initiator systems comprising a complexed initiator and a β-ketone compound decomplexer. The invention further relates to the use of these initiator systems for initiating polymerization, as well as kits, bonding compositions, and polymerized compositions made therewith, and coated substrates and bonded articles prepared therefrom.

CROSS REFERENCE TO RELATED APPLICATION

This application is a divisional of U.S. application Ser. No.10/037,074, filed Dec. 31, 2001, now allowed, the disclosure of which isherein incorporated by reference.

FIELD

This invention relates generally to systems capable of initiatingpolymerization. More specifically, the invention relates to initiatorsystems comprising a complexed initiator and a decomplexer. Theinvention further relates to the use of these initiator systems forinitiating polymerization, as well as kits, bonding compositions, andpolymerized compositions made therewith, and coated substrates andbonded articles prepared therefrom.

BACKGROUND

Systems for initiating the polymerization of monomers to make adhesivecompositions are known in the art. U.S. Pat. Nos. 5,106,928, 5,286,821,and 5,310,835 to Skoultchi et al., for example, describe two-partinitiator systems for initiating the polymerization of acrylic monomers.The first part of these two-part systems includes a stable organoboraneamine complex and the second part includes an activator. The activatorliberates the organoborane compound by removing the amine group, therebyallowing the organoborane compound to initiate the polymerizationprocess. Activators are also sometimes referred to as liberators ordecomplexers.

U.S. Pat. No. 5,286,821 to Skoultchi describes that suitable activatorsfor liberating the organoborane compound include aldehydes having thegeneral structure:R—(CHO)_(x)wherein R is an alkyl group having 1 to 10 carbon atoms or an aryl grouphaving 6 to 10 carbon atoms and x is 1 to 2. Examples includebenzaldehyde; o-, m-, p-nitrobenzaldehyde; 2,4-dichlorobenzaldehyde;p-tolylaldehyde; and 3-methoxy-4 hydroxybenzaldehyde.

U.S. Pat. Nos. 5,310,835 and 5,106,928 describes that suitableactivators for liberating the organoborane compound also include organicacids having the structure:R—COOHwherein R is H, an alkyl group, or an alkenyl group having 1 to 8 carbonatoms. Examples include acrylic acid, methacrylic acid, benzoic acid,and p-methoxybenzoic acid.

Fujisawa, Imai, and Mashuhara also describe a system for initiating thepolymerization of methyl methacrylate (See, Reports of the Institute forMedical and Dental Engineering, vol. 3, page 64 (1969)). The systemcomprises a trialkylborane amine complex and an activator such as thechloride of methacrylic or n-butane sulfonic acid, terephthalic acidchloride, benzoyl chloride, p-toluene sulfonic acid chloride, benzenesulfonic acid chloride, methane sulfonic acid chloride, toluenediisocyanate, adipic acid chloride, o-tolyl isocyanate, acetyl chloride,and acetic acid anhydride. The initiator system is reportedly useful inproviding fast curing resins for dental applications.

One disadvantage of some of the aforementioned activators, however, isthe relatively high odor of the activators and the composition in whichthey are used. Furthermore, another disadvantage of some of theseactivators is the relatively high level of mobile activator-aminereaction products (i.e., activator-amine constituents) in resultingadhesives. Typically, activators liberate the organoborane compound bybonding (either covalently or ionically) to the amine to form anactivator-amine constituent. Most activator-amine constituents remain inthe adhesive composition as mobile constituents that are notincorporated into the polymerized adhesive per se. In general, mobileconstituents in adhesive compositions may cause performance problemswhen, for example, they migrate to the surface of the adhesive therebydisrupting the bond interface. Mobile constituents are also susceptibleto attack by solvents, thereby making the adhesive composition lesssuitable for applications where exposure to solvents is unavoidable.

Recently, it has been disclosed that certain activators are useful forreducing the level of mobile constituents in adhesive compositionspolymerized therewith. For example, PCT Publication No. WO 97/07171discloses bireactive decomplexers preferably comprising at least onefree-radically polymerizable group and at least one amine-reactivegroup, preferably an isocyanate group, in the same molecule. Thebireactive decomplexers are capable of forming a covalent bond with bothacrylic monomers and the amine portion of the organoborane aminecomplex. Accordingly, the decomplexer is capable of covalently bondingto the liberated amine in the system and also reacting into the adhesiveper se.

PCT Publication No. WO 97/17383 discloses decomplexers comprising atleast one anhydride group. Preferred anhydrides have one of thefollowing structures:

wherein R₁ and R₂ may independently be an aliphatic group; acycloaliphatic group; or an aromatic group. R₃ is a divalent organicradical that completes a cyclic structure with the anhydride group. Itis further preferred that the decomplexer comprises at least one freeradically polymerizable group that is capable of forming a covalent bondwith an acrylic monomer, such that the decomplexer-amine reactionproduct is capable of forming covalent bonds with acrylic monomer(s) andcan be incorporated into the polymerized adhesive per se.

PCT Publication No. WO 99/64475 reports that suitable activators forliberating the organoborane compound also include carboxylic acidshaving the structure represented below:

wherein:

R¹ is selected from the group consisting of hydrogen, a monovalentorganic group, and a multivalent organic group;

R² is a multivalent organic group;

R³ is selected from the group consisting of hydrogen and a monovalentorganic group;

R is a monovalent organic group comprising an alkyl group having atleast nine carbon atoms, preferably at least 15 carbon atoms;

m is an integer of 0-2; and

n is an integer greater than or equal to one.

The previously reported decomplexing agents including, for example,carboxylic acids, carboxylic acid chlorides, carboxylic acid anhydrides,aldehydes, isocyanates, and sulfonyl chlorides can be corrosive,irritating or hydrolytically unstable materials. In addition, thesepreviously disclosed decomplexing agents generally react quickly withorganoborane-amine complexes, thereby quickly freeing the organoboranefor initiation of free radical polymerization. Rapid initiation of freeradical polymerization may lead to an undesirably short worklife of thebonding composition. In view of the foregoing, what is needed is asubstantially non-corrosive, non-irritating, storage stable decomplexingagent which preferably reacts slowly with an organoborane-amine complex,slowly freeing organoborane for initiation of free radicalpolymerization, and thus providing longer bonding composition worklife.

SUMMARY

Initiator systems of the present invention comprise both a complexedinitiator (e.g., an organoborane amine complex) and a β-ketone compounddecomplexer. Initiator systems of the present invention are particularlysuitable for preparing bonding compositions having a long worklife.

In one embodiment, the present invention provides an initiator systemcomprising:

a complexed initiator; and

a β-ketone compound decomplexer having a structure represented byformula (1) or formula (2):

wherein for formula (1):

R¹ is hydrogen or an organic group;

R² is an organic group;

W² is an electron withdrawing group selected from the group consistingof —O₂C—, —(CO)—, —HN(CO)—, and —NR³(CO)—; where R³ is an organic group;

R⁴ is an organic group having valence n; and

n is an integer greater than zero;

and wherein for formula (2):

R¹ is hydrogen or an organic group;

R² is an organic group; and

W¹ is an electron withdrawing group selected from the group consistingof NC— and H₂N(CO)—.

In another embodiment, the β-ketone compound decomplexers may bedescribed as acetoacetates or acetoacetamides. Acetoacetate decomplexershave the formula:

and acetoacetamides decomplexers have the formulas:

where the various substituents are as described above.

Representative examples of β-ketone compound decomplexers include methylacetoacetate, ethyl acetoacetate, t-butyl acetoacetate,2-methacryloyloxyethyl acetoacetate, diethylene glycolbis(acetoacetate), polycaprolactone tris(acetoacetate), polypropyleneglycol bis(acetoacetate), poly(styrene-co-allyl acetoacetate),N,N-dimethylacetoacetamide, N-methylacetoacetamide, acetoacetanilide,ethylene bis(acetoacetamide), polypropylene glycol bis(acetoacetamide),acetoacetamide, and acetoacetonitrile.

In another embodiment, the initiator system further comprises a seconddecomplexer. The second decomplexer may be, for example, anotherβ-ketone compound decomplexer, or it may be, for example, an anhydridedecomplexer. Preferred anhydride decomplexers are methacrylic anhydride,succinic anhydride, maleic ahhydride, glutaric anhydride, itaconicanhydride, and hexahydrophthalic anhydride.

In another embodiment, the present invention provides a bondingcomposition comprising:

(1) a polymerizable composition comprising:

-   -   at least one polymerizable monomer, and    -   a β-ketone compound decomplexer having a structure represented

by formula (1) or formula (2) (as set forth above); and

(2) a complexed initiator (preferably a complexed organoboraneinitiator).

The bonding composition may optionally include a metal salt modifier.Representative examples of metal salts include copper (II) bromide,copper (II) chloride, copper (II) 2-ethylhexanoate, iron (III) bromide,vanadium (III) bromide, chromium (III) bromide, ruthenium (III) bromide,copper (II) tetrafluoroborate, copper (II) trifluoromethanesulfonate,copper (II) naphthenate, copper (I) bromide, iron (II) bromide,manganese (II) bromide, cobalt (II) bromide, nickel (II) bromide,antimony (III) bromide, and palladium (II) bromide.

The β-ketone compound decomplexers are useful in kits that comprise apolymerizable composition (which includes the decomplexer and at leastone polymerizable monomer) and an initiator component (which includesthe complexed initiator and an optional diluent) for polymerizing thepolymerizable composition. Such kits are useful for bonding low surfaceenergy substrates. For ease of application, the kits can furthercomprise a multi-part dispenser. Once the parts of the kit are mixedtogether, bonding compositions are obtained. The bonding compositionscan be at least partially coated onto a substrate, preferably a lowsurface energy substrate. Once polymerized, a polymerized composition isobtained. The polymerized composition can be used to adhere a first andsecond substrate together in a bonded article.

As used herein the terms “monovalent organic group” and “multivalentorganic group” mean an organic moiety wherein the available valenciesare on carbon atoms. Monovalent organic groups have one availablevalency. Accordingly, multivalent organic groups have more than oneavailable valency.

As used herein the term “organic groups” can be aliphatic groups orcyclic groups. In the context of the present invention, the term“aliphatic group” means a saturated or unsaturated, linear or branched,hydrocarbon group. This term is used to encompass alkylene, alkenylene,alkynylene, alkyl, alkenyl, and alkynyl groups, for example. The term“alkyl group” means a monovalent, saturated, linear or branched,hydrocarbon group (e.g., a methyl, ethyl, isopropyl, t-butyl, heptyl,dodecyl, octadecyl, amyl, or 2-ethylhexyl group, and the like). The term“alkylene” means a multivalent, saturated, linear or branchedhydrocarbon group. The term “alkenyl group” means a monovalent,unsaturated, linear or branched, hydrocarbon group with one or morecarbon-carbon double bonds (e.g., a vinyl group). The term “alkenylene”means a multivalent, unsaturated, linear or branched, hydrocarbon groupwith one or more carbon-carbon double bonds. The term “alkynyl group”means a monovalent, unsaturated, linear or branched, hydrocarbon groupwith one or more carbon-carbon triple bonds. The term “alkynylene” meansa multivalent, linear or branched, hydrocarbon group with one or morecarbon-carbon triple bonds.

The term “cyclic group” means a closed ring hydrocarbon group that isclassified as an alicyclic group, aromatic group, or heterocyclic group.The term “alicyclic group” means a cyclic hydrocarbon group havingproperties resembling those of aliphatic groups. The term “aromaticgroup” or “aryl group” means a mononuclear aromatic hydrocarbon group orpolynuclear aromatic hydrocarbon group.

Organic groups or organic linking groups, as used herein, can includeheteroatoms (e.g., O, N, or S atoms), such as in the case ofheterocyclic groups, as well as functional groups (e.g., carbonylgroups).

DETAILED DESCRIPTION

This invention provides initiator systems capable of initiatingpolymerization. More specifically, the invention provides “initiatorsystems” comprising (1) a complexed initiator (e.g., an organoboraneamine complex) and (2) a β-ketone compound decomplexer. By utilizingβ-ketone functional groups on the decomplexers, as compared topreviously reported decomplexers, the decomplexers of the presentinvention typically react more slowly with a complexed initiator therebyproviding longer bonding composition worklife.

In one aspect of the invention, the initiator system is part of amulti-part kit. Such kits comprise at least a first part (i.e., apolymerizable composition) and a second part (i.e., an initiatorcomponent) for initiating polymerization of the polymerizablecomposition. Most preferably, for ease of use, the kits comprise onlytwo parts. The two parts of the kit may be readily combined in aconvenient, commercially useful, whole number mix ratio of 1:10 or less,more preferably 1:4, 1:3, 1:2 or 1:1, such that they can be easily usedwith multi-part dispensers. Such dispensers are shown in U.S. Pat. Nos.4,538,920 and 5,082,147 and are available from ConProTec, Inc. (Salem,N.H.) under the trade designation, MIXPAC. The parts of the kit can bereadily mixed to form bonding compositions, which readily polymerize topolymers, for example, adhesives.

The “polymerizable composition” typically comprises at least oneβ-ketone compound decomplexer and at least one polymerizable monomer.Optionally, another type of decomplexer, for example, carboxylic acids,carboxylic acid chlorides, carboxylic acid anhydrides, aldehydes,isocyanates, and sulfonyl chlorides may also be included in thepolymerizable composition. Most preferably, the decomplexer is arelatively low odor decomplexer.

“Low odor decomplexers” are those that have less odor than methylmethacrylate. Odor can be quantitatively measured using known methods,such as, for example, ASTM D4339-95, “Standard Test Method forDetermination of the Odor of Adhesives.”

The “initiator component” typically comprises at least one complexedinitiator (e.g., organoborane amine complex) and an optional diluent.When mixed with the polymerizable composition, the decomplexer in thepolymerizable composition liberates the initiator (e.g., organoborane)from the complexer (e.g., amine), enabling polymerization of the monomerto be initiated.

“Bonding compositions” are those compositions resulting from mixing ofthe polymerizable composition and the initiator component. The bondingcompositions are useful for bonding a wide variety of substrates,including polymers, wood, ceramics, concrete, and metals. The bondingcompositions are especially useful for bonding low-surface energysubstrates.

“Low surface energy substrates” are those that have a surface energy ofless than 45 mJ/m², more typically less than 40 mJ/m² or less than 35mJ/m². Included among such materials are polytetrafluoroethylene,polyethylene, and polypropylene. Other polymers of somewhat highersurface energy that may be usefully bonded with the compositions of theinvention include polycarbonate and polymethylmethacrylate. However, theinvention is not so limited; the compositions may be used to bond anythermoplastic, as well as wood, ceramics, concrete, primed metals, andthe like.

“Polymerized compositions” (also referred to as polymers) are thosebonding compositions where substantially all of the monomers in thepolymerizable composition are polymerized except for a typicallyunpolymerized amount as recognizable to one of ordinary skill in theart. Polymerized compositions according to the invention may be used ina wide variety of ways, including as adhesives, bonding materials,sealants, coatings, and injection molding resins. They may also be usedas matrix resins in conjunction with glass, carbon, and metal fibermats, such as those used in resin transfer molding operations. They mayfurther be used as encapsulants and potting compounds, such as in themanufacture of electrical components, printed circuit boards, and thelike. Decomplexer

The term “decomplexer” means a compound capable of liberating theinitiator (e.g., organoborane) from its complexer (e.g., amine), therebyenabling initiation of the polymerization process. Decomplexers are alsosometimes referred to as “activators” or “liberators.” As used herein,each of these terms has the same meaning.

In the present invention, the decomplexer has a β-ketone group that iscapable of forming a covalent bond with the amine portion of theorganoborane amine complex to liberate the organoborane compound.Hereinafter, such decomplexers will be referred to as β-ketone compounddecomplexers. Examples of such β-ketone compound decomplexers includemolecules comprising a single β-ketone group (see, formula 2) andmolecules comprising two or more β-ketone groups (see, formula 1).β-ketone compound decomplexers useful in the present invention may berepresented by formula (1) or formula (2):

wherein for formula (1):

R¹ is hydrogen or an organic group, preferably hydrogen;

R² is an organic group, preferably an aliphatic group, more preferably amethyl group;

W² is an electron withdrawing group selected from the group consistingof —O₂C—, —(CO)—, —HN(CO)—, and —NR³(CO)—; preferably W² is selectedfrom the group consisting of —O₂C—, —HN(CO)—, and

—NR³(CO)—; wherein R³ is an organic group;

R⁴ is an organic group having valence n; and

n is an integer greater than zero;

and wherein for formula (2):

R¹ is hydrogen or an organic group, preferably hydrogen;

R² is an organic group, preferably an aliphatic group, more preferably amethyl group; and

W¹is an electron withdrawing group selected from the group consisting ofNC— and H₂N(CO)—.

Preferred β-ketone compound decomplexers may be described asacetoacetates and acetoacetamides. Preferred acetoacetate decomplexershave the formula:

and preferred acetoacetamides decomplexers have the formulas:

where the various substituents are as described above.

Preferred β-ketone compounds have β-ketone equivalent weights less thanabout 550 grams/mole. That is, preferred β-ketone decomplexing agentsbearing a single β-ketone moiety (see formula 2) will have molecularweights less than about 550 grams/mole and preferred β-ketonedeomplexing agents bearing “n” β-ketone groups (see formula 1) will havea molecular weight less than about 550×n grams/mole.

Specific β-ketone compounds of formula (1) include, for example, methylacetoacetate, ethyl acetoacetate, t-butyl acetoacetate,2-methacryloyloxyethyl acetoacetate, diethylene glycolbis(acetoacetate), polycaprolactone tris(acetoacetate), polypropyleneglycol bis(acetoacetate), poly(styrene-co-allyl acetoacetate),N,N-dimethylacetoacetamide, N-methylacetoacetamide, acetoacetanilide,ethylene bis(acetoacetamide) and polypropylene glycolbis(acetoacetamide).

Specific β-ketone compounds of formula (2) include, for example,acetoacetamide and acetoacetonitrile.

Initiator systems and polymerizable compositions of the invention mayoptionally include more than one type of decomplexer. For example, theinitiator systems and polymerizable compositions may comprise, inaddition to a β-ketone compound decomplexer, one or more of theabove-described decomplexers and/or other decomplexers, such as thosecomprising at least one anhydride group as reported in PCT PublicationNo. WO 97/17383. Of those decomplexers reported in PCT Publication No.WO 97/17383, particularly useful anhydrides include methacrylicanhydride, succinic anhydride, maleic anhydride, and glutaric anhydride,itaconic anhydride, and hexahydrophthalic anhydride. Preferably, theβ-ketone compound decomplexer comprises at least about 10 weight % ofthe total decomplexer used. Most preferably, the β-ketone compounddecomplexer comprises at least about 50 weight % of the totaldecomplexers used.

When the initiator system includes an organoborane amine complex, thedecomplexer liberates organoborane from its amine complex by reactingwith the amine, thereby removing the organoborane from complexation withthe amine. Accordingly, the decomplexer is employed in an effectiveamount (i.e., an amount effective to promote polymerization byliberating organoborane from its amine complex, but without adverselyaffecting the material properties of the ultimate polymerizedcomposition).

As recognizable to one of ordinary skill in the art, larger amounts ofdecomplexer may permit polymerization to proceed too quickly and, in thecase of adhesives, the resulting materials may demonstrate inadequateadhesion to low energy surfaces. However, if not enough decomplexer isused, the rate of polymerization may be too slow and the resultingpolymers may not be of adequate molecular weight for certainapplications. However, a reduced amount of decomplexer may be helpful inslowing the rate of polymerization if it is otherwise too fast. Thus,within these parameters, in the case of organoborane amine complexinitiators, the decomplexer is typically provided in an amount such thatthe ratio of amine-reactive groups in the decomplexer(s) (e.g., β-ketonegroups, acid groups or anhydride groups) to amine groups is in the rangeof 0.5:1.0 to 10.0:1.0, preferably in the range of 1.0:1.0 to 7.0:1.0.It should be noted that the number of amine groups includes both primaryand secondary amine groups.

Complexed Initiator

The organoborane initiates free-radical polymerization of thepolymerizable monomer to form a polymer that can be useful as an bondingcomposition, for example an acrylic adhesive. The organoborane initiatormay be represented by the following general formula:

where R⁵ is an alkyl group having 1 to about 10 carbon atoms. R⁶ and R⁷may be the same or different and are independently selected from alkylgroups having 1 to about 10 carbon atoms and aryl groups. Preferably,R⁵, R⁶ and R⁷ are independently selected from alkyl groups having 1 toabout 5 carbon atoms. Accordingly, R⁵, R⁶ and R⁷ may all be different,or more than one of R⁵, R⁶ and R⁷ may be the same. Together, R⁵, R⁶ andR⁷, along with the boron atom (B) to which they are attached, form theinitiator. Specific organoborane initiators include, for example,trimethylborane, triethylborane, tri-n-propylborane, triisopropylborane,tri-n-butylborane, triisobutylborane, and tri-sec-butylborane.

Preferably, organoborane initiators are complexed with a complexingagent and may be represented by the following general formula:

wherein R⁵, R⁶ and R⁷ are as described above and wherein Cx is acomplexing agent.

Complexing Agents:

Useful complexing agents (Cx) include, for example, amines, amidines,hydroxides and/or alkoxides. The ratio of boron atoms to complexingagent (Cx) in the complex is represented by “v” and is preferablyselected so as to provide an effective ratio of the complexing agent andboron atoms. The boron atom to complexing agent ratio in the complex ispreferably about 1:1. A boron atom to complexing agent ratio of greaterthan 1:1 could leave free organoborane, a material that tends to bepyrophoric.

Amine Complexing Agents:

Amine complexing agents (Cx) may be provided by a wide variety ofmaterials having at least one amine group, including blends of differentamines. Amine complexing agents may also be polyamines (i.e., materialshaving two or more amine groups such as two to four amine groups).

In one embodiment the amine complexing agent may be a primary orsecondary monoamine, such as those represented by the structure:

wherein R⁸ and R⁹ are independently selected from the group consistingof hydrogen and organic groups, preferably alkyl groups having 1 to 10carbon atoms, alkylaryl groups in which the amine group is not directlyattached to the aryl structure, and polyoxyalkylene groups.Alternatively, R⁸ and R⁹ together with the nitrogen atom to which theyare attached may be joined to form a 4 to 7 membered heterocyclic ring.Particular examples of these amines include ammonia, ethylamine,butylamine, hexylamine, octylamine, benzylamine, morpholine, piperidine,pyrrolidine, and polyoxyalkylene monoamines (e.g., JEFFAMINES fromHuntsman Chemical Company, such as M715 and M2005).

In another embodiment, the amine may be a polyamine such as thosedescribed by the structure:R⁹HN—R¹¹—NHR⁹wherein R⁹ is as defined above and wherein R¹¹ is an organic group,preferably a divalent alkylene, arylene or alkylarylene group. Preferredamong these materials are alkane diamines which may be branched orlinear, and having the general structure:

in which x is a whole number greater than or equal to 1, more preferablyabout 2 to 12, and each R¹² is independently a hydrogen or an alkylgroup. Particularly preferred examples of alkane diamines include1,2-ethanediamine, 1,3-propanediamine, 1,5-pentanediamine,1,6-hexanediamine, 1,12-dodecanediamine, 2-methyl-1,5-pentanediamine,3-methyl-1,5-pentanediamine, and isomers of these materials. Whilealkane diamines are preferred, other alkyl polyamines may be used suchas triethylene tetraamine and diethylene triamine.

Useful polyamines may also be provided by a polyoxyalkylenepolyamine.Polyoxyalkylenepolyamines suitable in making complexes for the inventionmay be selected from the following structures:H₂NR¹³(R¹⁴O)_(w)—(R¹⁵O)_(x)—(R¹⁴O)_(y)—R¹³NH₂(i.e., polyoxyalkylene diamines); or[H₂NR¹³—(R¹⁴O)_(w)]_(z)—R¹⁶.R¹³, R¹⁴ and R¹⁵ are alkylene groups having 1 to 10 carbon atoms and maybe the same or may be different. Preferably, R¹³ is an alkylene grouphaving 2 to 4 carbon atoms such as ethylene, n-propylene, iso-propylene,n-butylene or iso-butylene. Preferably, R¹⁴ and R¹⁵ are alkylene groupshaving 2 or 3 carbon atoms such as ethylene, n-propylene oriso-propylene. R¹⁶ is the residue of a polyol used to prepare thepolyoxyalkylenepolyamine (i.e., the organic structure that remains ifthe hydroxyl groups are removed). R¹⁶ may be branched or linear, andsubstituted or unsubstituted (although substituents should not interferewith oxyalkylation reactions).

The value of w is ≧1, more preferably about 1 to 150, and mostpreferably about 1 to 20. The value of x and y are both ≧0. The value ofz is >2, more preferably 3 or 4 (so as to provide, respectively,polyoxyalkylene triamines and tetraamines). It is preferred that thevalues of w, x, y and z be chosen such that the resulting complex is aliquid at room temperature (“room temperature” refers to, herein, atemperature of about 20 to 25° C.) as this simplifies handling andmixing thereof. Usually, the polyoxyalkylenepolyamine is itself aliquid. For the polyoxyalkylenepolyamine, molecular weights of less thanabout 5,000 may be used, although molecular weights of about 1,000 orless are more preferred, and molecular weights of about 140 to 1,000 aremost preferred.

Examples of particularly preferred polyoxyalkylenepolyamines includepolyethyleneoxidediamine, polypropyleneoxidediamine,polypropyleneoxidetriamine, diethyleneglycoldipropylamine,triethyleneglycoldipropylamine, polytetramethyleneoxidediamine,poly(ethyleneoxide-co-propyleneoxide)diamine, andpoly(ethyleneoxide-co-propyleneoxide)triamine.

Examples of suitable commercially available polyoxyalkylenepolyaminesinclude various JEFFAMINES from Huntsman Chemical Company such as the D,ED, and EDR series diamines (e.g., D400, D-2000, D-5000, ED-600, ED-900,ED-2001, and EDR-148), and the T series triamines (e.g., T-403), as wellas DCA-221 from Dixie Chemical Company.

As reported in U.S. Pat. No. 5,616,796 (Pocius et al.), the disclosureof which is incorporated herein by reference, the polyamine may alsocomprise the condensation reaction product of diprimary amine-terminatedmaterial (i.e., the two terminal groups are primary amine) and one ormore materials containing at least two groups reactive with primaryamine.

Hydroxide/Alkoxide Complexing Agents:

Hydroxide and/or alkoxide complexing agents (Cx) are reported in PCTPublication WO 01/32716 (Moren), the disclosure of which is incorporatedherein by reference. Preferred hydroxide and/or alkoxide complexingagents may be represented by the formula:(⁻⁾O—R¹⁷)_(n)M^((m+))wherein:

R¹⁷ is independently selected from hydrogen or an organic group (e.g.,alkyl or alkylene group);

M^((m+)) represents a countercation (e.g., sodium, potassium,tetraalkylammonium, or combinations thereof);

n is an integer greater than zero; and

m is an integer greater than zero.

Amidine Complexing Agents:

Amidine complexing agents (Cx) are reported in PCT Publication WO01/32717 (Moren), the disclosure of which is incorporated herein byreference. Preferred amidine complexing agents may be represented by theformula:

wherein:

R¹⁸ is hydrogen or an organic group, preferably hydrogen or an alkyl oralkylene group;

R¹⁹ and R²⁰ are independently a monovalent organic group or part of acyclic structure; and

w, x, and y comprise integers, preferably w being 1 and x being about 3or less.

Particularly preferred amidine complexing agents comprise those selectedfrom the group consisting of N,N,N′,N′-tetramethylguanidine;1,8-diazabicyclo[5.4.0]undec-7-ene; 1,5-diazabicyclo[4.3.0]non-5-ene;2-methylimidazole; 2-methylimidazoline; and4-(N,N-dimethylamino)-pyridine.

An organoborane complex may be readily prepared using known techniques.Typically, the complexing agent is combined with the organoborane in aninert atmosphere (e.g., a glovebox flushed with nitrogen to anenvironment having less than 100 ppm oxygen) with slow stirring. Theorganoborane can be added from a pressure equalizing dropping funnel toa flask into which the coupling agent has been previously weighed. Anexotherm is often observed and cooling of the mixture is, therefore,recommended. Addition of the organoborane may be moderated to controlthe exotherm. If the ingredients have a high vapor pressure, it isdesirable to keep the reaction temperature below about 70° to 80° C.Once the materials have been well mixed the complex is permitted to coolto room temperature. No special storage conditions are required althoughit is preferred that the complex be kept in a capped vessel in a cool,dark location. A crystalline mass of the complex can be heated (e.g., toabout 55° C.) with an oil bath and outside of the nitrogen environmentto liquify the complex and facilitate its transfer to the storage vial,which can be flushed with nitrogen.

The organoborane is employed in an effective amount, which is an amountlarge enough to permit acrylic monomer polymerization to readily occurto obtain an acrylic polymer of high enough molecular weight for thedesired end use. If the amount of organoborane is too low, then thepolymerization may be incomplete or, in the case of adhesives, theresulting composition may have poor adhesion. On the other hand, if theamount of organoborane is too high, then the polymerization may proceedtoo rapidly to allow for effective mixing and use of the resultingcomposition.

Large amounts of organoborane could potentially weaken the bond formedby a bonding composition of the present invention. The useful rate ofpolymerization will depend in part on the method of applying thecomposition to a substrate. Thus, a faster rate of polymerization may beaccommodated by using a high speed automated industrial adhesiveapplicator rather than by applying the composition with a handapplicator or by manually mixing the composition.

Within these parameters, an effective amount of the organoborane is anamount that preferably provides about 0.003 to about 1.5 %-wt. boron,more preferably about 0.008 to about 0.5 %-wt. boron, most preferablyabout 0.01 to about 0.3 %-wt. boron. The %-wt. of boron in a compositionis based on the total weight of the composition, less fillers,non-reactive diluents, and other non-reactive materials. Thus, thepolymerizable monomers, the vinyl aromatic compound, and organicthickener, (e.g., poly(methyl methacrylate) or core-shell polymer), ifpresent, are included, but ingredients lacking abstractable hydrogenatoms or unsaturation are not. The %-wt. of boron in the composition maybe calculated by the following equation: $\frac{\begin{matrix}\left( {{weight}\quad{of}\quad{organoborane}} \right. \\\left. {{in}\quad{the}\quad{composition}} \right)\end{matrix} \times \begin{matrix}\left( {\%\text{-}{{wt}.\quad{of}}\quad{boron}} \right. \\\left. {{in}\quad{the}\quad{organoborane}} \right)\end{matrix}}{\left( {{Total}\quad{weight}\quad{of}\quad{the}\quad{composition}{less}\quad{non}\text{-}{reactive}\quad{components}} \right)}$

Diluent

The initiator component may also contain any suitable diluent, orcombination thereof, such as an aziridine-functional material (see, forexample, PCT Publication No. WO 98/17694), 1,4-dioxo-2-butene functionalmaterial (see, for example, U.S. Pat. No. 6,252,023) or a vinyl aromaticcompound (see, for example, PCT Publication WO 01/68783).

Generally, the diluent should not be reactive toward the complex andfunctions as an extender for the complex. Also advantageously, thediluent may generally increase the spontaneous combustion temperature ofthe initiator component.

The diluent should be generally soluble in monomers included in thepolymerizable composition, such that the parts of the kit can be readilymixed. By “soluble” is meant that no evidence of gross phase separationat room temperature is visible to the unaided eye. Similarly, theorganoborane amine complex should also be soluble in the diluent,although slightly warming a mixture of the complex and the diluent maybe helpful in forming a solution of the two at room temperature.Accordingly, preferably, if used, the diluent is a liquid at or nearroom temperature (i.e., within about 10° C. of room temperature) orforms a liquid solution with the organoborane amine complex at or nearroom temperature.

The diluent is used in an effective amount. Generally, this is an amountof not more than about 50 weight %, preferably not more than about 25weight %, more preferably not more than about 10 weight %, based on thetotal weight of the bonding composition.

Monomers

As stated previously, the initiator system of the invention can be usedto initiate the polymerization of any suitable monomer(s). Broadly, thepolymerizable composition includes at least one ethylenicallyunsaturated monomer capable of free radical polymerization. Numerouscompounds containing ethylenic unsaturation can be used in thepolymerizable composition. Preferably, the composition includes at leastone (meth)acrylic monomer, most preferably a methacrylic monomer. Asused herein the terms “(meth)acrylate” and “(meth)acrylic” and theplural forms thereof are meant to include both the acrylate andmethacrylate species of the designated compound. For example, the term“ethyl (meth)acrylate” is meant to include ethyl acrylate and ethylmethacrylate. Particularly preferred are (meth)acrylic acid derivatives,such as those including esters and/or (meth)acrylamides. Suitable are,for example, the (meth)acrylic esters of monohydric alcohols,particularly alkanols having from 1 to 12 carbon atoms, such as methyl(meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate,tetrahydrofurfuryl (meth)acrylate, and ethylhexyl (meth)acrylate; the(meth)acrylic acid esters of polyhydric alcohols, such as ethyleneglycol, diethylene glycol, polyethylene glycol, and trimethylol propane;the di- and mono(meth)acrylic acid esters of glycerin; thedi(meth)acrylic acid esters of triethylene glycol and tetraethyleneglycol; the di(meth)acrylic acid esters of dipropylene glycol,tripropylene glycol, tetrapropylene glycol and pentapropylene glycol;and the di(meth)acrylic esters of ethoxylated or propoxylateddiphenylolpropane.

Basically suitable are also polymerizable monomers, such as vinylacetate; vinyl halides, such as vinyl chloride, vinyl fluoride, vinylbromide; styrene; and divinyl-benzene. These compounds, however, aregenerally used only in subordinate amounts in the polymerizablecompositions.

Further suitable are (meth)acrylamides, such as: N,N-dimethylacrylamide,N,N-diethylacrylamide, N-butylacrylamide, N-(acryloyl)morpholine,N-(acryloyl)piperidine, and similar compounds.

In general, the emphasis is on monomers with one or two olefinic doublebonds in the molecule, preferably one olefinic double bond. Theadditional use of higher unsaturated components is not excluded, but itmust be kept in mind that their presence can lead to embrittling of thepolymerized compositions.

Additives

Bonding compositions of the present invention may also comprise optionaladditives. Such additives may be present in the polymerizablecomposition or in the initiator component of the kit. Thus, thepolymerizable composition and initiator component may further comprise avariety of optional additives.

One particularly useful additive is a thickener, such as medium (about40,000) molecular weight polybutyl methacrylate that may generally beincorporated in an amount of up to about 50 weight %, based on the totalweight of the bonding composition. Thickeners may be employed toincrease the viscosity of the resulting bonding composition to a moreeasily applied viscous syrup-like consistency.

Another particularly useful additive is an elastomeric material. Thesematerials can improve the fracture toughness of bonding compositionsmade therewith, which can be beneficial when, for example, bondingstiff, high yield strength materials (e.g., metal substrates that do notmechanically absorb energy as easily as other materials, such asflexible polymeric substrates). Such additives can generally beincorporated in an amount of up to about 50% by weight, based on thetotal weight of the bonding composition.

Core-shell polymers can also be added to the bonding composition tomodify spreading and flow properties of the bonding composition. Theseenhanced properties may be manifested by a reduced tendency for thebonding composition to leave an undesirable “string” upon dispensingfrom a syringe-type applicator, or sag or slump after having beenapplied to a vertical surface. Accordingly, use of more than about 20%by weight, based on total weight of the bonding composition, of acore-shell polymer additive may be desirable for achieving improvedsag-slump resistance.

Small amounts of inhibitors, such as hydroquinone monomethyl ether andtris(N-nitroso-N-phenylhydroxylamine) aluminum salt may be used in thepolymerizable compositions, for example, to prevent or reducedegradation of the monomers during storage. Inhibitors may be added inan amount that does not materially reduce the rate of polymerization orthe ultimate properties of polymers made therewith. Accordingly,inhibitors are generally useful in amounts of about 100-10,000 ppm basedon the total weight of the monomers in the polymerizable composition.

Other possible additives include non-reactive colorants, fillers (e.g.,carbon black, hollow glass/ceramic beads, silica, titanium dioxide,solid glass/ceramic spheres, and chalk), and the like. The variousoptional additives are employed in any amount, but generally amountsthat do not significantly adversely affect the polymerization process orthe desired properties of polymers made therewith.

Still other additives include metal salt modifiers such as thosereported, for example, in U.S. Pat. No. 6,734,2568 (Moren). Metal saltsmay be useful, for example, to modify the cure kinetics of the bondingcomposition to provide a favorable balance of long bonding compositionworklife and fast rate of strength build. Preferred metal salts includethose fitting the general formula:[M^(a+)L_(n)][X^(−m)]_(a/m)wherein:

M is a metal cation having two chemically accessible oxidation statesand having positive charge a, where a is an integer ranging from 1 to 6;

X is a counterion having charge −m, where m is an integer ranging from 1to 3;

L is a covalently bonded ligand; and

n is an integer ranging from 0 to 10 representing the number of ligandscovalently bonded to the metal cation.

Metal salts are generally useful in amounts of 60-20,000 ppm based onthe total weight of the bonding composition. Representative examples ofmetal salts include copper (II) bromide, copper (II) chloride, copper(II) 2-ethylhexanoate, iron (III) bromide, vanadium (III) bromide,chromium (III) bromide, ruthenium (III) bromide, copper (I)tetrafluoroborate, copper (II) trifluoromethanesulfonate, copper (II)naphthenate, copper (I) bromide, iron (II) bromide, manganese (II)bromide, cobalt (II) bromide, nickel (II) bromide, antimony (III)bromide, and palladium (II) bromide.

Bonding Compositions

The parts of the kits (i.e., the polymerizable composition and theinitiator component) are blended as would normally be done when workingwith such materials. The initiator component is added to thepolymerizable composition shortly before it is desired to use thebonding composition.

Once the parts of the kit have been combined to form a bondingcomposition, the composition should be used quickly, as the useful potlife may be short depending upon the monomers, the amount of theinitiator component, the presence or absence and identity of metal saltmodifiers, the temperature at which the bonding is to be performed, thepresence or absence of crosslinking agents, and whether a diluent isused. Preferably, to improve bonding, it is desirable to keep thetemperature below about 40° C.

The bonding composition is applied to one or both substrates to bebonded and then the substrates are joined together with pressure toforce excess bonding composition out of the bond line. This also has theadvantage of displacing bonding composition that has been exposed to airand that may have begun to oxidize. In general, the bonds should be madeshortly after the bonding composition has been applied to thesubstrate(s), preferably within about 60 minutes. The typical bond linethickness is about 0.1 to 0.3 millimeters.

The bonds may cure (i.e., polymerize) to a reasonable green strength,i.e., to permit handling of such bonded articles within about 2-6 hours.Full bond strength will generally be reached in less than 24 hours underambient conditions. However, post-curing with heat may be used, ifdesired.

In one preferred embodiment, the bonding compositions are coated on alow surface energy substrate. In another preferred embodiment, bondedarticles comprise a first substrate and a second substrate (preferablyat least one of which is a low surface energy polymeric material)adhesively bonded together by a layer of a bonding composition accordingto the invention.

The invention will be more fully appreciated with reference to thefollowing nonlimiting examples.

EXAMPLES

These examples are merely for illustrative purposes only and are notmeant to be limiting on the scope of the appended claims. All parts,percentages, ratios, etc. in the examples and the rest of thespecification are by weight unless indicated otherwise. Table ofAbbreviations Trade Designation or Other Abbreviation Description ARCALSAA100 poly(styrene-co-allyl alcohol), nominal Mn 1130, nominal Mw 2200,commercially available from ARCO Chemical Company; Newton Square, PA.t-BuAcAc t-butyl acetoacetate, commercially available from AldrichChemical Company; Milwaukee, WI. UrethHALL 5450A-220poly(2-methyl-1,3-propylene glutarate-co-2,2-dimethyl- 1,3-propyleneglutarate), nominal MW 510, commercially available from C. P. HallCompany; Chicago, IL. DEG diethylene glycol, commercially available fromAldrich Chemical Company; Milwaukee, WI. PCL triol polycaprolactonetriol, nominal molecular weight 300, commercially available from AldrichChemical Company; Milwaukee, WI. (catalog #20,038-7). ARCOL PPG2025polypropylene glycol, nominal molecular weight 2000, commerciallyavailable from ARCO Chemical Company; Newton Square, PA. TMI3-isopropenyl-α,α- dimethylbenzylisocyanate, commercially available fromCytec Industries, Inc.; West Peterson, NJ. Jeffamine D2000 amineterminated poly- propylene glycol, nominal molecular weight 2000,commercially available from Huntsman Petrochemical Corp; Houston, TX.triethylborane Commercially available from Aldrich Chemical Company;Milwaukee, WI. 1,6-hexanediamine Commercially available from AldrichChemical Company; Milwaukee, WI. Blendex 360 core-shell toughener,commercially available from GE Specialty Chemicals; Parkersburg, WV.THFMA tetrahydrofurfuryl methacrylate, commercially available fromSartomer Company; Exton, PA. DBI dibutyl itaconate, commerciallyavailable from Aldrich Chemical Company; Milwaukee, WI. Z-Light W1600ceramic microspheres (100-350 micron diameter), commercially availablefrom 3M Company; St. Paul, MN. MAEAcAc 2-methacryloyloxyethylacetoacetate, commercially available from Aldrich Chemical Company;Milwaukee, WI. ethyl acetoacetate Commercially available from AldrichChemical Company; Milwaukee, WI. 2,4-pentanedione Commercially availablefrom Aldrich Chemical Company; Milwaukee, WI. 4-hydroxycoumarinCommercially available from Aldrich Chemical Company; Milwaukee, WI.PhNHAcAc acetoacetanilide, Commercially available from Aldrich ChemicalCompany; Milwaukee, WI. 2-hydroxyethyl methacrylate Commerciallyavailable from Aldrich Chemical Company; Milwaukee, WI.2,6-di-t-butyl-4-methylphenol Commercially available from AldrichChemical Company; Milwaukee, WI. dibutyltin dilaurate Commerciallyavailable from Aldrich Chemical Company; Milwaukee, WI.2,4-Tolylenediisocyanate #43,348-9, nominal terminated polypropylenemolecular weight 1000, glycol commercially available from AldrichChemical Company; Milwaukee, WI. copper (II) bromide Available fromStrem Chemical Company, Newburyport, MA. N,N-dimethylacrylamideAvailable from Alfa-Aesar Company, Ward Hill, MA. HHPhAnhhexahydrophthalic anhydride, available from Aldrich Chemical Company.dibutyl maleate Available from C. P. Hall Company, Chicago, IL.

Adhesive Test Methods

Overlap Shear Bond Strength Test Method

Each bonding composition was applied directly onto an untreated 2.5cm×10 cm×0.3 cm (1 inch×4 inch×0.125 inch) test panel and an untreatedsecond test panel was immediately placed against the bonding compositionon the first test panel so that the overlapped area was 1.3 cm×2.5 cm(0.5 inch×1 inch). A clamp was applied to the overlapped area. The testpanels were high-density polyethylene (HDPE) (Minnesota Plastics;Minneapolis, Minn.). A small amount of bonding composition squeezed outof the overlapped area and was allowed to remain.

The bonds were allowed to cure for at least 48 hours at 22° C. Theclamps were then removed, and the overlap bonds were tested in shear(OLS) on a tensile tester at a crosshead speed of 1.27 cm/minute (0.5inch/minute). The overlap shear values were recorded in pounds persquare inch and were converted into megapascals (MPa). Overlap shearvalues represent the average of three replicates.

Worklife Test Method

This test measures overlap shear bond strength as a function of adhesiveair exposure time prior to bond formation. The Overlap Shear BondStrength Test Method above was followed, except that a bare second testpanel was not immediately pressed into the adhesive laden first testpanel, rather each bonding composition was applied directly onto anuntreated test panel, the assembly was allowed to stand in air for theOpen Time stated in the Examples, and then an untreated second testpanel was placed against the air-aged bonding composition on the firsttest panel to provide an overlapped area. The maximum Open Timeresulting in either 1) substrate yield without bond rupture or 2) bondrupture exhibiting 100% cohesive failure of the adhesive and resultingin an overlap shear value which is at least 95% of the overlap shearvalue measured according to the Overlap Shear Bond Strength Test Methodabove defines adhesive Worklife (also referred to as “WL”). Overlapshear values represent the average of two replicates.

Rate of Overlap Shear Bond Strength Increase Test Method

This test measures overlap shear bond strength of partially curedbonding composition as a function of cure time. The Overlap Shear BondStrength Test Method above was followed, except that the bonds were notallowed to cure for at least 48 hours at 22° C., rather the bonds wereallowed to cure at 22° C. for the time specified in the Examples. Theclamps were then removed, and the overlap bonds were tested in shear.The time to reach 50 psi (0.34 MPa) overlap shear strength was estimatedgraphically and is reported as “T50”. Overlap shear values represent theaverage of two replicates.

Hot Water Soak Overlap Shear Bond Strength Retention Test Method

This test measures overlap shear bond strength after hot water soak. TheOverlap Shear Bond Strength Test Method above was followed, except thatthe bonds were not tested immediately after curing for at least 48 hoursat 22° C. Rather the bonds were allowed to cure for at least 48 hours at22° C., the clamps were removed, the bonds were submerged in 70° C.water for 6 days, then the overlap bonds were tested in shear.

Peel Bond Strength Test Method

Each bonding composition was applied directly onto an untreated 0.8 mm(30 mil)-thick high-density polyethylene (HDPE) film (Cadillac Plastics;Minneapolis, Minn.). A second untreated HDPE film was pressed into thebonding composition and held in contact using a 1.2 kg (2.7 lb) weightedglass plate. Sufficient bonding composition was applied to the firstfilm to provide minimum bond dimensions of 2.5 cm (1 inch) in width by 5cm (2 inch) in length.

The bonded adherends were allowed to cure for 24 hours at 22° C. Thesamples were uncovered and allowed to cure at least 24 hoursadditionally at 22° C., then tested for bond strength in the T-peel modeusing a tensile tester set at a crosshead speed of 10.2 cm/min (4inches/min). Two overlapping free ends of the sample were clamped intothe jaws of the tensile tester, one free end in the upper jaw and onefree end in the lower jaw. The jaws were then pulled apart until atleast 2.5 cm (1 inch) of adhesive was exposed or until adherend failurewas observed. The average force per width during the run after theadhesive was initially exposed was recorded as the peel strength inpounds per inch and was converted into Newtons/cm (N/cm).

β-Ketone Functional Oligomer and Polymer Synthesis

SYNTHESIS EXAMPLE S1-POLY(STYRENE-CO-ALLYL ACETOACETATE) SYNTHESIS

ARCAL SAA100 (57.80 grams, 0.20 equivalents OH) and t-butyl acetoacetate(31.60 grams, 0.20 mole) were combined and heated to a 200° C. endpoint.t-Butyl alcohol distilled and was collected (14.35 grams, 97% oftheoretical). The poly(styrene-co-allyl acetoacetate) product cooled toa clear, hard glass. The adduct is hereinafter referred to“p(Sty-AAcAc)”.

SYNTHESIS EXAMPLES S2-S5

Synthesis Example S1 was repeated, but using various polyols in place ofARCAL SAA100 as shown in Table 1. t-Butyl alcohol recovery was greaterthan 95% of theoretical in each case. Synthesis Example S2-S5acetoacetate functional oligomer products were moderately viscousliquids. TABLE 1 Weight Synthesis Weight tBuAcAc Adduct Example Polyol(grams) (grams) Designation S2 UrethHALL 48.66 31.60 “5450AcAc2”5450A-220 S3 DEG 10.60 31.60 “DEGAcAc2” S4 PCL triol 20.00 31.60“PCLAcAc3” S5 ARCOL 1020.0 161.90 “PPGAcAc2” PPG2025

α-Methylstyrene Functional Oligomer Synthesis

SYNTHESIS EXAMPLE S6

TMI (120.60 grams, 0.60 mole) and Jeffamine D2000 (600.00 grams, 0.60equivalents NH₂) were combined and allowed to react without externaltemperature control. After standing at room temperature overnight,infrared spectroscopy indicated complete reaction by disappearance ofthe 2265 cm⁻¹ isocyanate band. The α-methylstyrene functional oligomerproduct is hereinafter referred to as “AMSPU2400”.

Methacrylate Terminated Polyurethane Synthesis

SYNTHESIS EXAMPLE S7

2,4-Tolylenediisocyanate terminated polypropylene glycol (493.00 grams,1.00 isocyanate equivalents), 2-hydroxyethyl methacrylate (143.14 grams,1.10 mole), 2,6-di-t-butyl-4-methylphenol (0.06 grams), and dibutyltindilaurate (0.30 grams) were combined sequentially and allowed to reactwithout external temperature control for one hour, then heated to 70° C.for four hours. Infrared spectroscopy indicated complete reaction bydisappearance of the 2265 cm⁻isocyanate band. The methacrylateterminated polyurethane product is hereinafter referred to as“PUMA1250”.

EXAMPLES 1-15

Initiator Component A

A 2:1 mole ratio triethylborane: 1,6-hexanediamine complex (32.00 grams)was dissolved in AMSPU2400 (168.00 grams). The air bubbles in theInitiator Component were allowed to rise and escape. This InitiatorComponent is hereafter referred to as “Initiator Component A”.

Polymerizable Composition

A slurry containing Blendex 360 (187.50 grams), THFMA (442.50 grams),DBI (56.25 grams), and AMSPU2400 (37.50 grams) was allowed to stand at70° C. for 2 hours. The resultant opaque dispersion was allowed to cooland then sheared aggressively with a saw-toothed blade of a laboratorydispersator, available from Premier Mill Corporation; Reading, Pa.Z-Light W1600 (15.00 grams) was added to the warm dispersion and mixedwell. This polymerizable composition is hereinafter referred to as“Monomer Blend A”.

A portion of the Monomer Blend A was combined with MAEAcAc or otherβ-ketone decomplexing agents as described in Table 2. Air bubbles wereremoved from the Polymerizable Compositions by briefly stirring undervacuum.

Adhesive

Each Polymerizable Composition and Initiator Component A were packagedin a 10:1 volume ratio dual syringe applicator (MixPac System 50, KitNo. MP-050-10-09, available from ConProTec; Salem, N.H.), the largercylinder holding the Polymerizable Composition and the smaller cylinderholding Initiator Component A. The two parts were combined bysimultaneous extrusion through a 10 cm (4 inch) long, 17-stage staticmix nozzle (Part No. MX 4-0-17-5, ConProTec). Test specimens wereprepared and tested according to the Test Methods outlined above, theresults are summarized in Table 3. In Table 4 the time to 50 psi (0.34MPa) HDPE OLS (T50), Worklife (WL) and the T50/WL ratio were estimatedfor Examples 1-15. TABLE 2 Weight Monomer Weight Blend A DecomplexerExample β-Ketone Decomplexer (grams) (grams) 1 MAEAcAc 45.83 4.17 2ethyl acetoacetate 49.33 0.67 3 MAEAcAc 48.90 1.10 4 p(Sty-AAcAc) 48.091.91 5 ethyl acetoacetate 46.40 3.60 6 5450AcAc2 48.32 1.68 7 5450AcAc241.61 8.39 8 DEGAcAc2 49.30 0.70 9 DEGAcAc2 46.49 3.51 10 PCLAcAc3 49.060.94 11 PCLAcAc3 45.28 4.72 12 p(Sty-AAcAc) 44.26 5.74 132,4-pentanedione 47.43 2.57 14 4-hydroxycoumarin 49.17 0.83 15Acetoacetanilide 49.09 0.91

TABLE 3 OLS @ OLS @ OLS @ OLS at OLS at OLS at HDPE HDPE 10 min 20 min30 min 90 min 120 min 150 min T-peel OLS Open Time Open Time Open Timecure cure cure Example (N/cm) (MPa) (MPa) (MPa) (MPa) (MPa) (MPa) (MPa)1 SB 6.74 6.71 3.10 3.90 0.67 NT NT 2 49 4.50 4.79 2.59 1.95 0.01 0.160.18 3 77 4.49 3.91 1.34 1.02 0.10 0.15 0.24 4 51 5.43 5.36 5.42 5.430.01 0.03 0.12 5 54 5.30 5.67 5.18 4.43 0.19 0.33 0.45 6 63 6.45 5.825.21 2.79 0.04 0.10 0.29 7 53 5.08 5.28 4.41 1.68 0.20 0.43 0.54 8 396.42 6.01 3.66 5.11 0.10 0.14 0.40 9 82 6.39 6.14 5.78 4.33 0.21 0.360.43 10 46 6.50 5.61 4.79 4.67 0.07 0.12 0.30 11 72 6.48 6.12 5.66 3.280.17 0.31 0.76 12 51 5.37 5.72 5.99 5.39 0.05 0.07 0.09 13 72 4.61 4.681.46 4.37 0.08 0.20 0.32 14 SB 6.79 6.42 6.56 4.79 0.27 0.41 0.77 15 636.66 5.50 3.31 2.08 0.28 0.39 0.57NT signifies that performance was not tested,SB signifies that the substrate broke

TABLE 4 T50 Worklife Example (minutes) (minutes) T50/WL ratio 1 72 107/1 2 180 10 18/1  3 172 10 17/1  4 202 30 7/1 5 123 20 6/1 6 156 30 5/17 120 20 6/1 8 145 30 5/1 9 132 20 7/1 10 156 30 5/1 11 120 20 6/1 12243 30 8/1 13 154 <10 >15/1  14 107 <10 >11/1  15 110 <10 >11/1 

EXAMPLES 16-18

A slurry containing Blendex 360 (187.50 grams), THFMA (442.50 grams),DBI (56.25 grams), and PUMA1250 (37.50 grams) was allowed to stand at70° C. for 2 hours. The resultant opaque dispersion was allowed to cooland then sheared aggressively with a saw-toothed blade of a laboratorydispersator. Z-Light W1600 (15.00 grams) was subsequently added to thewarm dispersion and mixed well. This polymerizable composition ishereinafter referred to as “Monomer Blend B”.

Polymerizable Compositions were prepared as in Examples 1-15, exceptreplacing Monomer Blend A with Monomer Blend B, and using the β-ketonedecomplexer whose identity and amount used is shown in Table 5. TABLE 5Weight Monomer Weight Blend B Decomplexer Example Decomplexer Identity(grams) (grams) 16 ethyl acetoacetate 49.33 0.67 17 MAEAcAc 48.90 1.1018 p(Sty-AAcAc) 48.09 1.91

Each Polymerizable Composition above was packaged opposite InitiatorComponent A of Examples 1-15. Test specimens were prepared and testedaccording to the Test Methods outlined above. The results are summarizedin Table 6. In Table 7 the time to 50 psi (0.34 MPa) HDPE OLS (T50),Worklife (WL) and the T50/WL ratio were estimated for Examples 16-18.TABLE 6 OLS @ OLS @ OLS @ HDPE HDPE 10 min 20 min 30 min OLS at OLS atOLS at T-peel OLS Open Time Open Time Open Time 90 min 120 min 150 minExample (N/cm) (MPa) (MPa) (MPa) (MPa) cure (MPa) cure(MPa) cure (MPa)16 18 6.12 1.31 3.08 1.72 0.13 0.27 0.43 17 2 6.00 4.66 0.56 0.06 0.180.21 0.21 18 SB 6.83 6.79 6.74 6.68 0.24 0.27 0.38SB signifies that the substrate broke

TABLE 7 T50 WL Example (minutes) (minutes) T50/WL ratio 16 135 <10 >13/117 ND <10 ND 18 159 30    5/1 ND signifies that a value was not determined

Hot Water Soak Overlap Shear Bond Strength Retention

The adhesives of Example 1 and Example 18 were tested as described inthe Hot Water Soak Overlap Shear Bond Strength Retention Test Method.The results are summarized in Table 8. TABLE 8 HDPE OLS After 6 Days 70°C. Water Soak Example (MPa) 1 6.66 18 6.60

EXAMPLES 19-28

Polymerizable Composition

A slurry containing Blendex 360 (202.50 grams), THFMA (511.50 grams),and AMSPU2400 (19.50 grams) was allowed to stand at 70° C. for 2 hours.The resultant opaque dispersion was allowed to cool and then shearedaggressively with a saw-toothed blade of a laboratory dispersator,available from Premier Mill Corporation; Reading, Pa. Z-Light W1600(16.50 grams) was added to the warm dispersion and mixed well. Thismonomer blend is hereinafter referred to as “Monomer Blend C”.

A slurry of copper (II) bromide (4.00 grams) in dimethylacrylamide (4.00grams) was heated to form a homogeneous black solution. This copper (II)bromide solution is hereinafter referred to as “Metal Salt Solution A”.In some Examples a second copper (II) bromide solution, “Metal SaltSolution B”, was used. Metal Salt Solution B was prepared by combining0.20 grams of Metal Salt Solution A with 0.80 grams dimethylacrylamide.

To prepare each example, Monomer Blend C was combined with MAEAcAc and aportion of Metal Salt Solution A or Metal Salt Solution B to form aPolymerizable Composition as described in Table 9. Air bubbles wereremoved from the Polymerizable Composition by briefly stirring undervacuum.

Adhesive

Each Polymerizable Composition and Initiator Component A were packagedin a 10:1 volume ratio dual syringe applicator (MixPac System 50, KitNo. MP-050-10-09, available from ConProTec; Salem, N.H.), the largercylinder holding the Polymerizable Composition and the smaller cylinderholding the Initiator Component. The two parts were combined bysimultaneous extrusion through a 10 cm (4 inch) long, 17-stage staticmix nozzle (Part No. MX 4-0-17-5, ConProTec). Test specimens wereprepared and tested according to the Test Methods outlined above, theresults are presented in Tables 10-12. In Table 13 the time to 0.34 MPaHDPE OLS (T50), Worklife (WL) and the T50/WL ratio were estimated forExamples 19-28. TABLE 9 Copper (II) Bromide Weight Monomer Weight Weight(grams) Concentration Blend C MAEAcAc and Identity of in PolymerizableExample (grams) (grams) Metal Salt Solution Composition (PPM) 19 45.774.18 0.05 Metal Salt Solution A 500 20 45.79 4.18 0.03 Metal SaltSolution B 60 21 45.76 4.18 0.06 Metal Salt Solution B 120 22 45.70 4.180.12 Metal Salt Solution B 240 23 45.72 4.18 0.10 Metal Salt Solution A1000 24 45.62 4.18 0.20 Metal Salt Solution A 2000 25 44.82 4.18 1.00Metal Salt Solution A 10,000 26 43.82 4.18 2.00 Metal Salt Solution A20,000 27 41.82 4.18 4.00 Metal Salt Solution A 40,000 28 37.82 4.188.00 Metal Salt Solution A 80,000

TABLE 10 HDPE OLS PP OLS Example (MPa) (MPa) 19 6.69 NT 20 5.89 1.90 216.12 1.54 22 6.09 1.72 23 6.39 NT 24 6.78 1.66 25 5.86 NT 26 5.94 NT 270.73 NT 28 0.21 NTNT signifies that performance was not tested

TABLE 11 OLS at OLS at OLS at OLS at OLS at OLS at OLS at 10 min 20 min30 min 40 min 45 min 50 min 60 min Open Time Open Time Open Time OpenTime Open Time Open Time Open Time Example (MPa) (MPa) (MPa) (MPa) (MPa)(MPa) (MPa) 19 6.09 6.63 6.61 6.63 NT 6.15 6.09 20 5.62 2.54 0.49 NT NTNT NT 21 6.10 5.99 2.41 NT NT NT NT 22 5.93 6.11 6.08 2.62 NT NT NT 236.66 6.63 6.63 6.64 NT 6.61 6.54 24 6.66 6.31 6.04 NT NT 6.61 6.48 25 NTNT 6.00 NT 6.03 NT 5.92 26 NT NT 5.68 NT 5.99 NT 5.97 27 NT NT 2.76 NT2.52 NT 1.50 28 NT NT 0.50 NT 0.89 NT 0.63NT signifies that performance was not tested.

TABLE 12 OLS at OLS at OLS at OLS at OLS at OLS at OLS at OLS at OLS atOLS at 45 min. 60 min. 75 min. 90 min. 105 min. 120 min. 135 min. 150min. 165 min. 180 min. cure cure cure cure cure cure cure cure cure cureExample (MPa) (MPa) (MPa) (MPa) (MPa) (MPa) (MPa) (MPa) (MPa) (MPa) 19 00.03 0.12 0.62 2.70 NT NT NT NT NT 20 0.14 0.20 0.55 1.08 1.64 NT NT NTNT NT 21 0.05 0.11 0.36 0.70 1.26 NT NT NT NT NT 22 0 0.06 0.23 0.921.59 NT NT NT NT NT 23 0.01 0.03 0.15 0.84 1.63 NT NT NT NT NT 24 NT0.01 NT NT 0.17 0.66 2.92 NT NT NT 25 NT NT NT NT 0.01 0.04 0.09 0.170.22 0.90 26 NT NT NT NT 0.09 0.12 0.26 0.31 0.39 0.92 27 NT NT NT NT NTNT NT NT NT NT 28 NT NT NT NT NT NT NT NT NT NTNT signifies that performance was not tested.

TABLE 13 Worklife T50 Example (minutes) (minutes) T50/WL ratio 19 60 841.4/1 20 10 65 6.5/1 21 20 75 3.8/1 22 30 84 2.8/1 23 60 84 1.4/1 24 60108 1.8/1 25 60 168 2.8/1 26 60 158 2.6/1 27 ND ND ND 28 ND ND NDND signifies that a value was not determined

EXAMPLES 29-51

Different metal salt solutions were prepared as described in Table 14according to the metal salt solution preparation description presentedin Examples 19-28 above. All metal salts are commercially available fromStrem Chemical Company, Newburyport, Mass. TABLE 14 Weight Dimethyl-Metal Salt Solution Weight Metal Salt (grams) acrylamide Designation andIdentity of Metal Salt (grams) Metal Salt Solution C 4.00 CuCl₂-2H₂O8.00 Metal Salt Solution D 4.00 4.00 Cu(O₂CCH(Et)(CH₂)₃CH₃)₂ Metal SaltSolution E 4.00 FeBr₃ 4.00 Metal Salt Solution F 4.00 FeCl₃ 6.00 MetalSalt Solution G 0.50 VBr₃ 1.50 Metal Salt Solution H 0.50 CrBr₃-6H₂O1.50 Metal Salt Solution I 0.50 RuBr₃-xH₂O 1.50 Metal Salt Solution J0.50 Cu(BF₄)₂ 1.50 Metal Salt Solution K 0.50 Cu(O₃SCF₃)₂ 1.50 MetalSalt Solution L 0.50 1.50 Cu(naphthenate)₂ Metal Salt Solution M 1.00CuBr 9.00 Metal Salt Solution N 1.00 FeBr₂ 2.00 Metal Salt Solution O0.50 MnBr₂ 1.50 Metal Salt Solution P 0.50 CoBr₂-xH₂O 1.50 Metal SaltSolution Q 0.50 NiBr₂-xH₂O 1.50 Metal Salt Solution R 0.50 SbBr₃ 1.50Metal Salt Solution S 0.50 PdBr₂ 9.50

Polymerizable Compositions were prepared as in Examples 19-28 exceptreplacing Metal Salt Solution A with varying amounts of Metal SaltSolution C to S. Each Polymerizable Composition was packaged oppositeInitiator Component A, as in Examples 19-28. Test specimens wereprepared and tested according to the Test Methods outlined above. Theresults are summarized in Tables 16-20. In Table 11 the time to 0.34 MPa(50 psi) HDPE OLS (T50), Worklife (WL) and the T50/WL ratio wereestimated for Examples 29-51. TABLE 15 Weight Monomer Weight Weight(grams) Blend C MAEAcAc and Identity of Example (grams) (grams) MetalSalt Solution 29 45.59 4.18 0.23 Metal Salt Solution C 30 45.50 4.180.32 Metal Salt Solution D 31 45.55 4.18 0.27 Metal Salt Solution E 3245.64 4.18 0.18 Metal Salt Solution F 33 45.30 4.18 0.52 Metal SaltSolution G 34 45.10 4.18 0.72 Metal Salt Solution H 35 45.12 4.18 0.70Metal Salt Solution I 36 45.39 4.18 0.43 Metal Salt Solution J 37 45.174.18 0.65 Metal Salt Solution K 38 44.72 4.18 1.10 Metal Salt Solution L39 45.17 4.18 0.65 Metal Salt Solution M 40 44.52 4.18 1.30 Metal SaltSolution M 41 45.53 4.18 0.29 Metal Salt Solution N 42 45.38 4.18 0.44Metal Salt Solution N 43 45.76 4.18 0.06 Metal Salt Solution E 44 45.744.18 0.08 Metal Salt Solution I 45 45.70 4.18 0.12 Metal Salt Solution L46 45.75 4.18 0.03 Metal Salt Solution N 47 45.43 4.18 0.39 Metal SaltSolution O 48 45.33 4.18 0.49 Metal Salt Solution P 49 45.33 4.18 0.49Metal Salt Solution Q 50 45.17 4.18 0.65 Metal Salt Solution R 51 43.424.18 2.40 Metal Salt Solution S

TABLE 16 HDPE OLS PP OLS Example (Mpa) (MPa) 29 6.70 1.20 30 6.14 0.3731 6.78 1.66 32 3.86 4.14 33 5.86 NT 34 5.61 NT 35 1.77 NT 36 5.68 NT 375.75 NT 38 1.61 NT 39 5.89 NT 40 5.94 NT 41 3.03 NT 42 1.86 NT 43 5.97NT 44 5.93 NT 45 5.48 NT 46 5.85 NT 47 5.69 NT 48 3.14 NT 49 2.66 NT 505.92 NT 51 5.83 NTNT signifies that performance was not tested

TABLE 17 OLS at OLS at OLS at OLS at OLS at OLS at OLS at 10 min 20 min30 min 40 min 45 min 50 min 60 min Open Time Open Time Open Time OpenTime Open Time Open Time Open Time Example (MPa) (MPa) (MPa) (MPa) (MPa)(MPa) (MPa) 29 6.71 6.30 6.53 6.61 NT 5.19 3.79 30 4.76 5.25 4.78 4.59NT 3.17 1.78 31 6.31 2.82 NT NT NT NT NT 32 6.40 3.97 NT NT NT NT NT 333.77 4.01 1.26 NT NT NT NT 34 5.63 3.41 2.12 NT NT NT NT 35 2.29 1.671.37 NT 1.45 NT 1.53 36 4.16 2.39 0.58 NT 1.68 NT NT 37 3.19 0.96 0.08NT NT NT NT 38 1.22 0.40 0.19 NT 0.34 NT NT 39 5.89 5.97 5.92 NT 5.80 NT5.81 40 5.90 5.90 5.88 NT 5.30 NT 5.59 41 5.77 5.62 3.91 NT 1.10 NT 1.5042 4.95 4.68 2.89 NT 1.95 NT 1.44 43 6.05 4.58 2.28 NT NT NT NT 44 5.945.72 4.33 NT NT NT NT 45 5.28 4.57 0.80 NT NT NT NT 46 5.91 4.63 2.52 NTNT NT NT 47 5.84 5.84 5.64 NT NT NT NT 48 0.70 2.75 2.58 NT NT NT NT 490.74 3.03 4.30 NT NT NT NT 50 5.88 5.52 4.50 NT NT NT NT 51 5.25 1.460.57 NT NT NT NTNT signifies that performance was not tested

TABLE 18 OLS at OLS at OLS at OLS at OLS at OLS at OLS at OLS at 45 min.60 min. 75 min. 90 min. 105 min. 120 min. 135 min. 150 min. Example cure(MPa) cure (MPa) cure (MPa) cure (MPa) cure (MPa) cure (MPa) cure (MPa)cure (MPa) 29 0.01 0.01 0.02 0.12 0.46 2.59 NT NT 30 NT NT NT NT NT NTNT NT 31 NT NT NT NT NT NT NT NT 32 NT NT NT NT NT NT NT NT 33 0.11 0.541.14 2.28 3.28 4.36 NT NT 34 0.08 0.10 0.16 0.11 0.21 0.41 NT NT 35 NTNT NT NT NT NT NT NT 36 0.06 0.26 1.46 4.86 5.35 5.28 NT NT 37 0.08 0.383.33 5.79 5.60 5.89 NT NT 38 0.06 0.98 1.26 1.23 0.95 1.32 NT NT 39 0 00 0 0.03 0.12 1.93 NT 40 0 0 0 0 0 0.04 0.43 NT 41 0.03 0.05 0.04 0.100.09 0.14 0.20 0.26 42 0.01 0 0.01 0 0 0.04 0.19 0.05 43 0.08 0.15 0.230.35 0.37 0.48 NT NT 44 0.05 0.14 0.24 0.28 0.42 0.52 NT NT 45 0.10 0.431.57 2.81 3.21 4.00 NT NT 46 0.04 0.15 0.19 0.28 0.41 0.47 NT NT 47 0.060.10 0.25 0.58 0.75 1.68 NT NT 48 0.14 0.24 0.68 0.62 1.10 1.98 NT NT 490.14 0.12 0.28 0.34 0.43 0.51 NT NT 50 0.12 0.17 0.27 0.28 0.48 0.68 NTNT 51 0.08 0.15 0.34 0.62 0.85 1.32 NT NTNT signifies that performance was not tested.

TABLE 19 Worklife T50 Example (minutes) (minutes) T50/WL ratio 29 40 1012.5/1 30 <10 ND ND 31 10 ND ND 32 <10 ND ND 33 <10 55 >5.5/1  34 10 120 12/1 35 ND ND ND 36 <10 65 >6.5/1  37 <10 60  >6/1 38 ND 55 ND 39 60123   2/1 40 60 134 2.2/1 41 10 ND ND 42 10 ND ND 43 10 96 9.6/1 44 1096 9.6/1 45 <10 58 >5.8/1  46 10 96 9.6/1 47 20 81   4/1 48 <10 71  >7/149 <10 87 >8.7/1  50 10 86 8.6/1 51 <10 75 >7.5/1 ND signifies that a value was not determined

EXAMPLES 52-55

Examples 52-55 were prepared and evaluated as in Examples 19-28, exceptdifferent Polymerizable Compositions and Initiator Components were used.

Two Initiator Components were prepared.

Initiator Component B

Poly(butyl methacrylate-co-methyl methacrylate) (Aldrich #47,403-7;molecular weight 150,000) (4.00 grams) and dibutyl maleate (6.00 grams)were combined and heated to form a solution. A 2:1 mole ratiotriethylborane:1,6-hexanediamine complex (1.90 grams) was added to thecooled polymer solution and then gently heated under a nitrogenatmosphere to form a homogeneous solution. The air bubbles were allowedto rise and escape. This solution is hereinafter referred to as“Initiator Component B”.

Initiator Component C

A slurry containing Blendex 360 (18.05 grams) and dibutyl maleate (33.51grams) was allowed to stand at 70° C. for 2 hours. The resultant opaquedispersion was allowed to cool and then sheared aggressively with asaw-toothed blade of a laboratory dispersator, available from PremierMill Corporation; Reading, Pa. A 2:1 mole ratiotriethylborane:1,6-hexanediamine complex (1.90 grams) and a portion ofthis dispersion (10.00 grams) were combined and gently heated under anitrogen atmosphere to form a homogeneous dispersion. The air bubbleswere allowed to rise and escape. This dispersion is hereinafter referredto as “Initiator Component C”.

Polymerizable Compositions

A slurry containing Blendex 360 (58.41 grams) and THFMA (161.59 grams)was allowed to stand at 70° C. for 2 hours. The resultant opaquedispersion was allowed to cool and then sheared aggressively with asaw-toothed blade of a laboratory dispersator, available from PremierMill Corporation; Reading, Pa. This monomer blend is hereinafterreferred to as “Monomer Blend D”. Two Polymerizable Compositions wereprepared as in Examples 19-28 using the components shown in Table 20.TABLE 20 Weight Monomer Weight Weight Weight Metal Weight PolymerizableBlend D MAEAcAc PUMA1250 Salt Solution A Z-light W1600 Composition(grams) (grams) (grams) (grams) (grams) A 89.34 8.36 0 0.10 2.20 B 79.348.36 10.00 0.10 2.20

Each of Polymerizable Compositions A and B were packaged opposite eachof Initiator Components B and C, as shown in Table 21 using the methoddescribed in Examples 19-28. Test specimens were prepared and testedaccording to the Test Methods outlined above. The results are summarizedin Tables 21-23. In Table 24 the time to 0.34 MPa HDPE OLS (T50),Worklife (WL) and the T50/WL ratio were estimated for Examples 52-55.TABLE 21 Initiator Polymerizable HDPE T-peel HDPE OLS PP OLS ExampleComponent Composition (N/cm) (MPa) (MPa) 52 B A 21 5.87 2.21 53 B B SB5.86 2.36 54 C A 19 5.84 2.81 55 C B SB 5.83 2.71SB signifies that the substrate broke

TABLE 22 OLS at OLS at OLS at OLS at OLS at 10 min 20 min 30 min 45 min60 min Open Time Open Time Open Time Open Time Open Time Example (MPa)(MPa) (MPa) (MPa) (MPa) 52 5.76 5.88 5.82 5.31 3.86 53 5.85 5.82 5.853.28 3.71 54 5.81 5.79 5.81 5.92 4.54 55 5.75 5.85 5.61 4.94 NTNT signifies that performance was not tested.

TABLE 23 OLS at 45 OLS at 60 OLS at 75 OLS at 90 OLS at 105 minutesminutes minutes minutes minutes Example cure (MPa) cure (MPa) cure (MPa)cure (Mpa) cure (MPa) 52 0 0.01 0.11 0.39 1.09 53 0 0.06 0.14 0.49 0.7454 0 0 0.08 0.39 1.13 55 0.01 0.05 0.19 0.59 1.79

TABLE 24 Worklife T50 Example (minutes) (minutes) T50/WL ratio 52 30 883/1 53 30 88 3/1 54 45 88 2/1 55 30 81 2.7/1  

EXAMPLES 56-59

Polymerizable Compositions were prepared as in Examples 19-28, exceptwith various decomplexers as shown in Table 25. Each PolymerizableComposition was packaged opposite Initiator Component A, as in Examples19-28. Test specimens were prepared and tested according to the TestMethods outlined above. The results are shown in Tables 27-29. In Table30 the time to 0.34 MPa HDPE OLS (T50), Worklife (WL) and the T50/WLratio were estimated for Examples 38-44. TABLE 25 Weight Weight (grams)Weight Metal Monomer Blend and Identity of Salt Solution A Example C(grams) Decomplexer (grams) 56 43.62 6.33 DEGAcAc₂ 0.05 57 40.38 9.57p(Sty-AAcAc) 0.05 58 42.27 7.68 MAEAcAc 0.05 59 48.89 0.91 PhNHAcAc 0.20

EXAMPLES 60-68

A slurry of copper (II) bromide (5.00 grams) in dimethylacrylamide(15.00 grams) was heated to form a homogeneous black solution. Thiscopper (II) bromide solution is hereinafter referred to as “Metal SaltSolution T”.

Hexahydrophthalic anhydride (10.00 grams) was dissolved in THFMA (15.00grams). This solution was used to prepare Examples 47-58.

Polymerizable Compositions were prepared as in Examples 1-10, exceptwith a different decomplexer (hexahydrophthalic anhydride), andreplacing Metal Salt Solution A with Metal Salt Solution T as shown inTable 26. Each Polymerizable Composition was packaged opposite InitiatorComponent A, as in Examples 19-28. Test specimens were prepared andtested according to the Test Methods outlined above. The results areshown in Tables 27-29. In Table 30 the time to 0.34 MPa HDPE OLS (T50),Worklife (WL) and the T50/WL ratio were estimated for Examples 47-58.TABLE 26 Weight Weight Weight Monomer HHPhAnh Weight Metal Salt Blend Csolution MAEAcAc Solution T Example (grams) (grams) (grams) (grams) 6047.66 0.99 1.25 0.10 61 47.17 1.48 1.25 0.10 62 49.06 0.69 0.15 0.10 6348.89 0.69 0.32 0.10 64 48.57 0.69 0.64 0.10 65 45.88 0.05 3.97 0.10 6646.03 0.10 3.77 0.10 67 46.35 0.19 3.36 0.10 68 46.96 0.39 2.55 0.10

TABLE 27 HDPE T-peel HDPE OLS PP OLS Example (N/cm) (MPa) (MPa) 56 584.11 3.96 57 37 5.87 5.12 58 SB 5.86 3.54 59 NT 5.61 0.94 60 SB 6.568.03 61 SB 6.54 8.08 62 SB 6.52 7.27 63 SB 6.48 7.77 64 SB 6.46 7.97 65SB 6.11 2.65 66 SB 6.61 2.45 67 SB 6.63 3.01 68 SB 6.61 3.73NT signifies that performance was not tested,SB signifies that the substrate broke

TABLE 28 OLS at OLS at OLS at OLS at OLS at 10 min 20 min 30 min 45 min60 min Open Time Open Time Open Time Open Time Open Time Example (MPa)(MPa) (MPa) (MPa) (Mpa) 56 4.29 3.83 3.51 3.10 1.91 57 5.52 5.58 5.695.59 5.34 58 5.87 5.92 5.86 5.54 2.73 59 4.77 4.01 3.38 NT NT 60 5.493.72 2.05 NT NT 61 4.39 3.39 1.53 NT NT 62 6.49 6.33 4.61 NT NT 63 6.455.73 4.38 NT NT 64 6.49 5.59 3.41 NT NT 65 6.63 6.61 6.24 6.52 6.63 666.60 6.67 6.62 6.56 4.50 67 6.57 5.99 6.50 5.27 NT 68 5.94 6.28 2.97 NTNTNT signifies that performance was not tested.

TABLE 29 OLS at OLS at OLS at OLS at OLS at OLS at OLS at OLS at OLS at45 min. 60 min. 75 min. 90 min. 105 min. 120 min. 135 min. 150 min. 180min. cure cure cure cure cure cure cure cure cure Example (MPa) (MPa)(MPa) (MPa) (MPa) (MPa) (MPa) (MPa) (MPa) 56 NT NT NT NT NT NT NT NT NT57 NT NT NT NT NT NT NT NT NT 58 0 0.02 0.14 0.52 1.55 NT NT NT NT 59 NTNT NT NT NT NT NT NT NT 60 0.15 0.49 0.50 0.99 NT NT NT NT NT 61 0.120.26 0.38 0.55 NT NT NT NT NT 62 0.08 0.15 0.36 0.31 NT NT NT NT NT 630.07 0.17 0.46 0.54 NT NT NT NT NT 64 0.09 0.39 0.61 0.54 NT NT NT NT NT65 0 0.01 0.08 0.26 1.10 NT NT NT NT 66 0 0.06 0.25 1.12 2.58 NT NT NTNT 67 0.04 0.27 0.85 2.62 5.94 NT NT NT NT 68 0.24 1.02 3.31 5.64 6.45NT NT NT NTNT signifies that performance was not tested.

TABLE 30 Worklife T50 Example (minutes) (minutes) T50/WL ratio 56 30 NDND 57 60 ND ND 58 45 85 1.9/1 59 30 ND ND 60 <10 62 >6.2/1   61 <1073 >7.3/1   62 20 77 3.9/1 63 10 70   7/1 64 10 61 6.1/1 65 60 91 1.5/166 45 76 1.7/1 67 30 62   2/1 68 15 47   3/1ND signifies that a value was not determined

The complete disclosures of the patents, patent documents, andpublications cited herein are incorporated by reference in theirentirety as if each were individually incorporated. Variousmodifications and alterations to this invention will become apparent tothose skilled in the art without departing from the scope and spirit ofthis invention. It should be understood that this invention is notintended to be unduly limited by the illustrative embodiments andexamples set forth herein and that such examples and embodiments arepresented by way of example only with the scope of the inventionintended to be limited only by the claims set forth herein as follows.

1. A kit comprising: (1) a polymerizable composition, wherein thepolymerizable composition comprises: at least one polymerizable monomer,and a β-ketone compound decomplexer having a structure represented byformula (1) or formula (2):

wherein for formula (1): R¹ is hydrogen or an organic group; R² is anorganic group; W² is an electron withdrawing group selected from thegroup consisting of —O₂C—, —(CO)—, —HN(CO)—, and —NR³(CO)—; where R³ isan organic group; R⁴ is an organic group having valence n; and n is aninteger greater than zero; and wherein for formula (2): R¹ is hydrogenor an organic group; R² is an organic group; and W¹ is an electronwithdrawing group selected from the group consisting of NC— andH₂N(CO)—; and (2) an initiator component, wherein the initiatorcomponent comprises: a complexed initiator, and an optional diluent. 2.The kit according to claim 1, further comprising a multi-part dispenser.3. A bonding composition comprising: (1) a polymerizable compositioncomprising: at least one polymerizable monomer, and a β-ketone compounddecomplexer having a structure represented by formula (1) or formula(2):

wherein for formula (1): R¹ is hydrogen or an organic group; R² is anorganic group; W² is an electron withdrawing group selected from thegroup consisting of —O₂C—, —(CO)—, —HN(CO)—, and —NR³(CO)—; where R³ isan organic group; R⁴ is an organic group having valence n; and n is aninteger greater than zero; and wherein for formula (2): R¹ is hydrogenor an organic group; R² is an organic group; and W¹is an electronwithdrawing group selected from the group consisting of NC— andH₂N(CO)—; and (2) a complexed initiator.
 4. The bonding composition ofclaim 3, wherein the decomplexer is an acetoacetamide decomplexer havinga structure represented by the following formulas:


5. The bonding composition of claim 3, wherein the decomplexer is anacetoacetate decomplexer having a structure represented by the followingformula:


6. The bonding composition of claim 3, wherein R¹ is hydrogen.
 7. Thebonding composition of claim 3, wherein R² is an aliphatic group.
 8. Thebonding composition of claim 3, wherein R² is a methyl group.
 9. Thebonding composition of claim 3, wherein W² is selected from the groupconsisting of —O₂C—, —HN(CO)—; and —NR³(CO)—.
 10. The bondingcomposition of claim 3, wherein the decomplexer is selected from thegroup consisting of methyl acetoacetate, ethyl acetoacetate, t-butylacetoacetate, 2-methacryloyloxyethyl acetoacetate, diethylene glycolbis(acetoacetate), polycaprolactone tris(acetoacetate), polypropyleneglycol bis(acetoacetate), poly(styrene-co-allyl acetoacetate),N,N-dimethylacetoacetamide, N-methylacetoacetamide, acetoacetanilide,ethylene bis(acetoacetamide), polypropylene glycol bis(acetoacetamide),acetoacetamide, and acetoacetonitrile.
 11. The bonding composition ofclaim 3 further including a second decomplexer.
 12. The bondingcomposition of claim 11, wherein the second decomplexer comprises ananhydride decomplexer.
 13. The bonding composition of claim 12, whereinthe second decomplexer is selected from the group consisting ofmethacrylic anhydride, succinic anhydride, maleic anhydride, glutaricanhydride, itaconic anhydride, and hexahydrophthalic anhydride
 14. Thebonding composition of claim 3, wherein the complexed initiator is anorganoborane complex.
 15. The bonding composition of claim 14, whereinthe organoborane complex has the structure represented by the followingformula:

wherein R⁵ is an alkyl group having 1 to about 10 carbon atoms; R⁶ and Rmay be the same or different and are independently selected from alkylgroups having 1 to about 10 carbon atoms and aryl groups; and Cx is acomplexing agent.
 16. The bonding composition of claim 14, wherein thecomplexing agent is selected from the group consisting of amines,amidines, hydroxides and alkoxides.
 17. The bonding composition of claim3 further comprising a diluent.
 18. The bonding composition of claim 3further including at least one optional additive.
 19. The bondingcomposition of claim 18, wherein the optional additive comprises a metalsalt modifier according to the general formula:[M^(a+)L_(n)][X^(−m)]_(a/m) where: M is a metal cation having twochemically accessible oxidation states and having positive charge a,where a is an integer ranging from 1 to 6; X is a counterion havingcharge −m, where m is an integer ranging from 1 to 3; L is a covalentlybonded ligand; and n is an integer ranging from 0 to 10 representing thenumber of ligands covalently bonded to the metal cation.
 20. The bondingcomposition of claim 19, wherein the metal salt modifier is selectedfrom the group consisting of copper (II) bromide, copper (II) chloride,copper (II) 2-ethylhexanoate, iron (III) bromide, vanadium (III)bromide, chromium (III) bromide, ruthenium (III) bromide, copper (II)tetrafluoroborate, copper (II) trifluoromethanesulfonate, copper (II)naphthenate, copper (I) bromide, iron (II) bromide, manganese (II)bromide, cobalt (II) bromide, nickel (II) bromide, antimony (III)bromide, and palladium (II) bromide.